CN110776627A - Polyester polyol for solvent-free adhesive and preparation method and application thereof - Google Patents
Polyester polyol for solvent-free adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN110776627A CN110776627A CN201911023922.3A CN201911023922A CN110776627A CN 110776627 A CN110776627 A CN 110776627A CN 201911023922 A CN201911023922 A CN 201911023922A CN 110776627 A CN110776627 A CN 110776627A
- Authority
- CN
- China
- Prior art keywords
- polyester polyol
- percent
- weight
- acid
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 40
- 239000000853 adhesive Substances 0.000 title claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 24
- 229920001451 polypropylene glycol Polymers 0.000 claims description 23
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- 239000001361 adipic acid Substances 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 5
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 2
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 claims description 2
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- LJAGLQVRUZWQGK-UHFFFAOYSA-N oxecane-2,10-dione Chemical compound O=C1CCCCCCCC(=O)O1 LJAGLQVRUZWQGK-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses polyester polyol for a solvent-free adhesive, and a preparation method and application thereof. The polyester polyol is prepared from the following components in percentage by weight: 35 to 55 percent of dicarboxylic acid or carboxylic anhydride, 20 to 40 percent of linear dihydric alcohol, 0.3 to 2.0 percent of dihydric alcohol containing side groups, 15 to 20 percent of polyether polyol and 1.0 to 3.0 percent of micromolecular polyhydric alcohol; the number of hydroxyl groups in the small molecular polyol molecule is more than or equal to 3. According to the invention, polyhydroxy is introduced into polyester polyol to improve the reaction activity, ether bond is introduced to improve the compatibility, and side group and ether bond are introduced to improve the hydrolysis resistance, so that the prepared polyester polyol has lower viscosity, good compatibility, higher reaction activity and hydrolysis resistance, is especially suitable for preparing solvent-free adhesive for high-speed compounding, quick curing, medium and high-end flexible packages, and can obviously improve the bonding force, heat resistance and weather resistance of the adhesive.
Description
Technical Field
The invention belongs to the field of adhesives, and relates to polyester polyol for a solvent-free adhesive, and a preparation method and application thereof.
Background
The polyester polyol is used for the adhesive for compounding the flexible package, can provide larger intermolecular force, enhances the adhesive force, improves the heat resistance and weather resistance, and improves the initial adhesion. The solvent-free flexible package is characterized in that the adhesive needs lower viscosity and good compatibility. When the conventional polyester polyol is used for a solvent-free adhesive, the conventional polyester polyol often has the quality problems that the adhesive is too high in viscosity, poor in hydrolysis resistance and poor in compatibility with materials such as polyether and the like, so that the gluing is difficult, the appearance of a finished product of a composite film is easy to dissolve in ink, the color and luster are dark, the bonding performance of an adhesive base layer after curing is not stable enough, the hydrolysis resistance is not high, and the like, and the requirements of high-speed compounding and quick curing medium-high-end solvent-free flexible packaging adhesives cannot be fully met.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides polyester polyol for a solvent-free adhesive and a preparation method thereof.
The technical scheme provided by the invention is as follows:
the polyester polyol is prepared from the following components in percentage by weight: 35 to 55 percent of dicarboxylic acid or carboxylic anhydride, 20 to 40 percent of linear dihydric alcohol, 0.3 to 2.0 percent of dihydric alcohol containing side groups, 15 to 20 percent of polyether polyol and 1.0 to 3.0 percent of micromolecular polyhydric alcohol; the number of hydroxyl groups in the small molecular polyol molecule is more than or equal to 3.
On the basis of the technical scheme, the linear dihydric alcohol is selected from one or more of ethylene glycol, diethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the diol containing side group is one or more selected from 2, 2-dimethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol and 2-butyl-2-ethyl-1, 3-propanediol.
On the basis of the technical scheme, the dicarboxylic acid is selected from one or more of succinic acid, adipic acid, azelaic acid, isophthalic acid and phthalic acid; the carboxylic anhydride is selected from one or more of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride and phthalic anhydride.
On the basis of the technical scheme, the polyether polyol is selected from one or more of polyethylene glycol, polypropylene oxide glycol and polytetrahydrofuran glycol.
On the basis of the technical scheme, the micromolecular polyalcohol is one or more selected from glycerol, trimethylolpropane, castor oil, pentaerythritol and xylitol.
A preparation method of polyester polyol comprises the following steps: under the protection of nitrogen, all the components in the proportion are added into a reactor, stirred and heated to 130-150 ℃, and the system is drained; continuously heating to 190 ℃ and 210 ℃, and adding the auxiliary agent when the temperature is kept until the acid value is less than 30 mgKOH/g; continuously heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g and the hydroxyl value is 70-250mgKOH/g, and stopping the reaction to obtain polyester polyol;
wherein the concentration of the auxiliary agent in the reaction liquid is 10-500 ppm; the auxiliary agent is one or more selected from stannous octoate, dibutyltin dilaurate, dibutyltin, tetrabutyl titanate, tetraisopropyl titanate and bismuth laurate.
On the basis of the technical scheme, the heating process is continuous heating or step heating.
On the basis of the technical scheme, the top temperature is controlled to be less than or equal to 103 ℃ in the temperature rising process.
The polyester polyol is applied to the preparation of the solvent-free adhesive.
The principle of the invention is as follows:
the invention belongs to a high polymer addition condensation reaction, water is generated and removed through the esterification reaction of acid and alcohol, and then by-products such as water and the like are removed through further condensation reaction of low molecular weight polyester under the conditions of catalyst, heating and the like to generate sticky substances with certain molecular weight; the invention introduces polyhydroxy into polyester polyol to improve the reaction activity, introduces ether bond to improve the compatibility, introduces side group and ether bond to improve the hydrolysis resistance, and enhances the intermolecular force between the adhesive and the base material.
The invention has the following advantages and beneficial effects:
the invention introduces micromolecular polyether polyol and diol containing side group in the synthesis of polyester polyol, improves the compatibility and hydrolysis resistance of the polyester polyol, widens the selectivity of raw materials in the development of solvent-free adhesives, introduces micromolecular polyether polyol on the basis to prepare the polyester polyol with low viscosity, higher reaction activity, good compatibility and hydrolysis resistance, can improve and improve the initial adhesion of the solvent-free adhesive, and is particularly suitable for the development and application of the solvent-free adhesive for high-speed compounding and rapid curing of medium and high-end flexible packages.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific examples, which are only for explaining the technical solutions of the present invention and are not used to limit the protection scope of the present invention.
Example 1
Adding 40.97 parts by weight of adipic acid, 6.87 parts by weight of isophthalic acid, 2.3 parts by weight of ethylene glycol, 32.59 parts by weight of diethylene glycol, 0.44 part by weight of 2, 2-dimethyl-1, 3-propanediol and 16.82 parts by weight of polypropylene glycol (PPG-400) into a reactor, stirring and heating to 150 ℃ under the protection of nitrogen, starting the reaction and discharging water from the system; continuously heating to 190 ℃ and 210 ℃, and adding tetra-n-butyl titanate (the concentration in the reaction solution is 30ppm) when the acid value is less than 30 mgKOH/g; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 2
Adding 39.91 parts by weight of adipic acid, 6.7 parts by weight of isophthalic acid, 2.24 parts by weight of ethylene glycol, 32.39 parts by weight of diethylene glycol, 0.43 part by weight of 2, 2-dimethyl-1, 3-propanediol, 1.94 parts by weight of trimethylolpropane and 16.39 parts by weight of polypropylene glycol (PPG-400) into a reactor, stirring and heating to 130-phase temperature of 150 ℃ under the protection of nitrogen, starting the reaction, and discharging water from the system; the temperature is continuously increased to 190 ℃ and 210 ℃, when the acid value is less than 30mgKOH/g, tetra-n-butyl titanate (the concentration in the reaction liquid is 50ppm) is added; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 3
Adding 39.28 parts by weight of adipic acid, 7.02 parts by weight of terephthalic acid, 2.35 parts by weight of ethylene glycol, 33.10 parts by weight of diethylene glycol, 0.44 part by weight of 2-butyl-2-ethyl-1, 3-propanediol, 0.66 part by weight of trimethylolpropane and 17.19 parts by weight of polypropylene glycol (PPG-1000) into a reactor, stirring and heating to 130-150 ℃ under the protection of nitrogen, starting the reaction, and discharging water from the system; the temperature is continuously raised to 190 ℃ and 210 ℃, and when the acid value is less than 30mgKOH/g, tetraisopropyl titanate (the concentration in the reaction liquid is 25ppm) is added; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 4
Adding 36.61 parts by weight of adipic acid, 8.61 parts by weight of isophthalic acid, 2.58 parts by weight of ethylene glycol, 38.76 parts by weight of diethylene glycol, 0.52 part by weight of 2, 2-dimethyl-1, 3-propanediol and 12.93 parts by weight of polypropylene glycol (PPG-400) into a reactor, stirring and heating to 150 ℃ under the protection of nitrogen, starting the reaction, and discharging water from the system; continuously heating to 190 ℃ and 210 ℃, and adding stannous octoate (the concentration in the reaction liquid is 60ppm) when the acid value is less than 30 mgKOH/g; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 5
Adding 39.89 parts by weight of adipic acid, 7.13 parts by weight of terephthalic acid, 32.01 parts by weight of diethylene glycol, 0.45 part by weight of 2-butyl-2-ethyl-1, 3-propanediol, 0.67 part by weight of glycerol and 17.76 parts by weight of polypropylene glycol (PPG-400) into a reactor, stirring and heating to 150 ℃ under the protection of nitrogen, starting the reaction and discharging water from the system; the temperature is continuously increased to 190 ℃ and 210 ℃, when the acid value is less than 30mgKOH/g, tetra-n-butyl titanate (the concentration in the reaction liquid is 60ppm) is added; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 6
Adding 37.95 parts by weight of adipic acid, 8.93 parts by weight of isophthalic acid, 2.23 parts by weight of ethylene glycol, 37.05 parts by weight of diethylene glycol, 0.42 part by weight of 2, 2-dimethyl-1, 3-propanediol and 13.40 parts by weight of polypropylene glycol (PPG-400) into a reactor according to 100 parts by weight of the total weight of the raw materials, stirring and heating to 130-150 ℃ under the protection of nitrogen, starting the reaction, and discharging water from the system; the temperature is continuously raised to 190 ℃ and 210 ℃, and when the acid value is less than 30mgKOH/g, tetraisopropyl titanate (the concentration in the reaction liquid is 60ppm) is added; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 7
Adding 38.46 parts by weight of adipic acid, 9.05 parts by weight of isophthalic acid, 2.26 parts by weight of 1, 2-propylene glycol, 36.20 parts by weight of diethylene glycol, 0.45 part by weight of 2, 2-dimethyl-1, 3-propylene glycol and 13.57 parts by weight of polypropylene glycol (PPG-1000) into a reactor, stirring and heating to 150 ℃ under the protection of nitrogen, and reacting to start to obtain water; continuously heating to 190 ℃ and 210 ℃, and adding stannous octoate (the concentration in the reaction liquid is 60ppm) when the acid value is less than 30 mgKOH/g; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 8
Adding 37.29 parts by weight of adipic acid, 8.77 parts by weight of terephthalic acid, 2.19 parts by weight of ethylene glycol, 36.41 parts by weight of diethylene glycol, 0.53 part by weight of 2, 2-dimethyl-1, 3-propanediol, 1.75 parts by weight of trimethylolpropane and 13.15 parts by weight of polypropylene glycol (PPG-400) into a reactor, stirring and heating to 130-phase temperature of 150 ℃ under the protection of nitrogen, starting the reaction and discharging water from the system; the temperature is continuously increased to 190 ℃ and 210 ℃, when the acid value is less than 30mgKOH/g, tetra-n-butyl titanate (the concentration in the reaction liquid is 60ppm) is added; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 9
Adding 36.21 parts by weight of adipic acid, 7.21 parts by weight of isophthalic acid, 4.53 parts by weight of ethylene glycol, 33.95 parts by weight of diethylene glycol, 0.68 part by weight of 2-butyl-2-ethyl-1, 3-propanediol and 17.61 parts by weight of polypropylene glycol (PPG-400) into a reactor, stirring and heating to 130-150 ℃ under the protection of nitrogen, starting the reaction and discharging water from the system; the temperature is continuously raised to 190 ℃ and 210 ℃, and when the acid value is less than 30mgKOH/g, tetraisopropyl titanate (the concentration in the reaction liquid is 60ppm) is added; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
Example 10
Adding 39.18 parts by weight of adipic acid, 6.62 parts by weight of isophthalic acid, 2.45 parts by weight of ethylene glycol, 32.03 parts by weight of diethylene glycol, 0.42 part by weight of 2, 2-dimethyl-1, 3-propanediol, 1.92 parts by weight of trimethylolpropane and 17.38 parts by weight of polypropylene glycol (PPG-400) into a reactor, stirring and heating to 130-phase temperature and 150 ℃ under the protection of nitrogen, and reacting to obtain water; the temperature is continuously increased to 190 ℃ and 210 ℃, when the acid value is less than 30mgKOH/g, tetra-n-butyl titanate (the concentration in the reaction liquid is 60ppm) is added; heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g, cooling and discharging to obtain the polyester polyol with qualified index characteristics.
The results of the performance tests of the polyester polyols synthesized in the above examples are shown in Table 1.
The method relating to the performance test of polyester polyol is as follows:
1) acid value measurement: tested according to HG/T2708-;
2) hydroxyl value determination: tested according to HG/T2709-;
3) and (3) measuring the color: testing according to GB/T605-;
4) and (3) viscosity measurement: testing according to the GB/T2794-2013 standard (rotational viscometer method);
5) and (3) water content determination: tested according to GB/T6283-2008 standard.
TABLE 1 measurement results of properties of polyester polyols prepared in examples 1 to 10
The above embodiments are merely for clearly illustrating the embodiments and are not intended to limit the embodiments. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (9)
1. The polyester polyol is characterized by being prepared from the following components in percentage by weight: 35 to 55 percent of dicarboxylic acid or carboxylic anhydride, 20 to 40 percent of linear dihydric alcohol, 0.3 to 2.0 percent of dihydric alcohol containing side groups, 15 to 20 percent of polyether polyol and 1.0 to 3.0 percent of micromolecular polyhydric alcohol; the number of hydroxyl groups in the small molecular polyol molecule is more than or equal to 3.
2. The polyester polyol according to claim 1, wherein: the linear dihydric alcohol is one or more of ethylene glycol, diethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol;
the dihydric alcohol containing the side group is one or more of 2, 2-dimethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol and 2-butyl-2-ethyl-1, 3-propanediol.
3. The polyester polyol according to claim 1, wherein: the dicarboxylic acid is one or more of succinic acid, adipic acid, azelaic acid, isophthalic acid and phthalic acid; the carboxylic anhydride is one or more of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride and phthalic anhydride.
4. The polyester polyol according to claim 1, wherein: the polyether polyol is one or more of polyethylene glycol, polypropylene glycol, polyoxypropylene glycol and polytetrahydrofuran glycol.
5. The polyester polyol according to claim 1, wherein: the micromolecular polyalcohol is one or more of glycerol, trimethylolpropane, castor oil, pentaerythritol and xylitol.
6. A method for preparing the polyester polyol according to any one of claims 1 to 5, comprising the steps of: under the protection of nitrogen, all the components in the proportion of any one of claims 1 to 5 are added into a reactor, stirred and heated to 130-150 ℃, and the system is drained; continuously heating to 190 ℃ and 210 ℃, and adding the auxiliary agent when the temperature is kept until the acid value is less than 30 mgKOH/g; continuously heating to 230 ℃ and keeping the temperature for reaction until the acid value is less than 2mgKOH/g and the hydroxyl value is 70-250mgKOH/g, and stopping the reaction to obtain polyester polyol;
wherein the concentration of the auxiliary agent in the reaction liquid is 10-500 ppm; the auxiliary agent is one or more of stannous octoate, dibutyltin dilaurate, dibutyltin, tetrabutyl titanate, tetraisopropyl titanate and bismuth laurate.
7. The method according to claim 6, characterized in that: the temperature rise process is continuous temperature rise or step temperature rise.
8. The method for preparing according to claim 7, characterized in that: the top temperature is controlled to be less than or equal to 103 ℃ in the temperature rising process.
9. Use of the polyester polyol according to any one of claims 1 to 5 for the preparation of solvent-free adhesives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911023922.3A CN110776627B (en) | 2019-10-25 | 2019-10-25 | Polyester polyol for solvent-free adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911023922.3A CN110776627B (en) | 2019-10-25 | 2019-10-25 | Polyester polyol for solvent-free adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110776627A true CN110776627A (en) | 2020-02-11 |
| CN110776627B CN110776627B (en) | 2022-03-18 |
Family
ID=69386601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911023922.3A Active CN110776627B (en) | 2019-10-25 | 2019-10-25 | Polyester polyol for solvent-free adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110776627B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533891A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
| CN112048278A (en) * | 2020-09-15 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Boiling-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof |
| CN112063352A (en) * | 2020-09-08 | 2020-12-11 | 湖北回天新材料(宜城)有限公司 | Low-odor solvent-free bi-component polyurethane adhesive and preparation method and application thereof |
| CN112708386A (en) * | 2020-12-24 | 2021-04-27 | 上海回天新材料有限公司 | Solvent-free single-component moisture-curing polyurethane adhesive for paper-plastic compounding and preparation method thereof |
| CN113150259A (en) * | 2020-12-28 | 2021-07-23 | 上海汇得科技股份有限公司 | Branched polyester polyol and preparation method and application thereof |
| CN113388096A (en) * | 2021-07-05 | 2021-09-14 | 英克化工科技（太仓）有限公司 | Polyester polyol for solvent-free adhesive and preparation method thereof |
| CN113528076A (en) * | 2020-12-31 | 2021-10-22 | 上海回天新材料有限公司 | Solvent-free single-component moisture-curing polyurethane adhesive for wearable equipment and preparation method thereof |
| CN114369236A (en) * | 2021-11-30 | 2022-04-19 | 山东一诺威新材料有限公司 | High-performance polyester ether polyol and preparation method and application thereof |
| CN114854475A (en) * | 2022-06-06 | 2022-08-05 | 广州润泰新材料科技有限公司 | Vegetable oil-based biodegradable lubricating oil with good stability and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044665A (en) * | 2013-01-05 | 2013-04-17 | 旭川化学（苏州）有限公司 | Hydrolysis-resistant polyester polyol and preparation method thereof |
| US20130210989A1 (en) * | 2010-10-01 | 2013-08-15 | Henkel Ag & Co. Kgaa | Polyurethane hot-melt adhesive produced from polyacrylates and polyesters |
| CN104817994A (en) * | 2015-04-27 | 2015-08-05 | 武汉戴尔惠科技有限公司 | Fast-cured composite adhesive and preparation method thereof |
| CN106497493A (en) * | 2016-09-29 | 2017-03-15 | 上海回天新材料有限公司 | One-component solvent-free type polyurethane adhesive and its preparation method and application |
| CN106520054A (en) * | 2016-11-16 | 2017-03-22 | 北京高盟新材料股份有限公司 | Low-friction-coefficient and solvent-free type polyurethane adhesive and preparation method thereof |
| CN110804158A (en) * | 2019-11-27 | 2020-02-18 | 南通高盟新材料有限公司 | Double-head coating solvent-free polyurethane adhesive and preparation method thereof |
-
2019
- 2019-10-25 CN CN201911023922.3A patent/CN110776627B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130210989A1 (en) * | 2010-10-01 | 2013-08-15 | Henkel Ag & Co. Kgaa | Polyurethane hot-melt adhesive produced from polyacrylates and polyesters |
| CN103044665A (en) * | 2013-01-05 | 2013-04-17 | 旭川化学（苏州）有限公司 | Hydrolysis-resistant polyester polyol and preparation method thereof |
| CN104817994A (en) * | 2015-04-27 | 2015-08-05 | 武汉戴尔惠科技有限公司 | Fast-cured composite adhesive and preparation method thereof |
| CN106497493A (en) * | 2016-09-29 | 2017-03-15 | 上海回天新材料有限公司 | One-component solvent-free type polyurethane adhesive and its preparation method and application |
| CN106520054A (en) * | 2016-11-16 | 2017-03-22 | 北京高盟新材料股份有限公司 | Low-friction-coefficient and solvent-free type polyurethane adhesive and preparation method thereof |
| CN110804158A (en) * | 2019-11-27 | 2020-02-18 | 南通高盟新材料有限公司 | Double-head coating solvent-free polyurethane adhesive and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533891A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
| CN112063352A (en) * | 2020-09-08 | 2020-12-11 | 湖北回天新材料(宜城)有限公司 | Low-odor solvent-free bi-component polyurethane adhesive and preparation method and application thereof |
| CN112048278A (en) * | 2020-09-15 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Boiling-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof |
| CN112048278B (en) * | 2020-09-15 | 2022-12-09 | 山东一诺威聚氨酯股份有限公司 | Steaming-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof |
| CN112708386A (en) * | 2020-12-24 | 2021-04-27 | 上海回天新材料有限公司 | Solvent-free single-component moisture-curing polyurethane adhesive for paper-plastic compounding and preparation method thereof |
| CN113150259A (en) * | 2020-12-28 | 2021-07-23 | 上海汇得科技股份有限公司 | Branched polyester polyol and preparation method and application thereof |
| CN113150259B (en) * | 2020-12-28 | 2022-07-29 | 上海汇得科技股份有限公司 | Branched polyester polyol and preparation method and application thereof |
| CN113528076A (en) * | 2020-12-31 | 2021-10-22 | 上海回天新材料有限公司 | Solvent-free single-component moisture-curing polyurethane adhesive for wearable equipment and preparation method thereof |
| CN113388096A (en) * | 2021-07-05 | 2021-09-14 | 英克化工科技（太仓）有限公司 | Polyester polyol for solvent-free adhesive and preparation method thereof |
| CN114369236A (en) * | 2021-11-30 | 2022-04-19 | 山东一诺威新材料有限公司 | High-performance polyester ether polyol and preparation method and application thereof |
| CN114369236B (en) * | 2021-11-30 | 2024-04-12 | 山东一诺威新材料有限公司 | High-performance polyester ether polyol, and preparation method and application thereof |
| CN114854475A (en) * | 2022-06-06 | 2022-08-05 | 广州润泰新材料科技有限公司 | Vegetable oil-based biodegradable lubricating oil with good stability and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110776627B (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110776627B (en) | Polyester polyol for solvent-free adhesive and preparation method and application thereof | |
| CN112063352B (en) | Low-odor solvent-free bi-component polyurethane adhesive and preparation method and application thereof | |
| CN103044665B (en) | Hydrolysis-resistant polyester polyol and preparation method thereof | |
| CN113710764B (en) | Two-component solvent-free polyurethane laminating adhesive composition | |
| AU2014301403B2 (en) | Hydrophobic polyurethane adhesive | |
| CN113980635B (en) | Adhesive for steaming-resistant food flexible package composite film, and preparation method and application thereof | |
| CN112143437A (en) | Lithium battery aluminum plastic film outer layer adhesive resin and preparation and application thereof | |
| KR102621143B1 (en) | Biodegradable adhesive composition | |
| CN116675840A (en) | Multifunctional polyester polyol for hydrolysis-resistant polyurethane structural adhesive | |
| CN113528076A (en) | Solvent-free single-component moisture-curing polyurethane adhesive for wearable equipment and preparation method thereof | |
| JPH08183943A (en) | Adhesive composition for dry laminating and dry laminating method using the same | |
| CN113667444B (en) | Solvent-free bi-component polyurethane adhesive and preparation method and application thereof | |
| CN117736684B (en) | Nano composite functional hot melt adhesive and manufacturing process thereof | |
| CN112142961B (en) | Tackifying additive and application thereof in aspect of woodworking glue | |
| CN110305283B (en) | Polyurethane adhesive for compounding polylactic acid film and aluminum foil | |
| CN113789146A (en) | High-oil-resistance high-temperature-cooking-resistant bi-component polyurethane adhesive and preparation method thereof | |
| CN116987473A (en) | Functional polyurethane adhesive and preparation method thereof | |
| CN111978909B (en) | Reactive polyurethane hot melt adhesive for low-temperature coating and preparation method thereof | |
| TW202307170A (en) | Adhesive composition and adhesive sheet | |
| CN112760076A (en) | Solvent-free two-component aluminum-plastic cooking glue and preparation method thereof | |
| TWI822673B (en) | Moisture-curable polyurethane hot-melt resin composition | |
| EP0652248A2 (en) | Modifier for synthetic resins | |
| CN111117544A (en) | Biodegradable pressure-sensitive adhesive and preparation method thereof | |
| KR102316790B1 (en) | Biodegradable polyester resin made by addition of biomass derived reaction rate control agent and molecular weight extender and the manufacturing method thereof | |
| CN115651590B (en) | Solvent-free polyurethane adhesive for industrial conveyor belt and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |